Partially dehalogenated reactive derivatives of the halogenation products of the mono hetero atomic five membered rings



Patented July 12, 1949 PARTIALLY DEHALOGENATED REACTIVE DERIVATIVES OF THE HALOGENATION PRODUCTS OF THE MONO HETERO ATOMIC FIVE MEMBERED RINGS Emil E. Novotny, Prospectville, and George Karl Vogelsang, LaMott, Pa., assignors,'by mesne assignments, to The Borden Company, New York, N. Y., a corporation of New Jersey No Drawing. Application November 21, 1942, Serial No. 466,480

8 Claims.

This invention relates to the partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings as well as to the methods for preparing said products.

In a more specific aspect, the invention relates to the partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydes of furan and its homologues as well as to the methods for preparing said products.

In a preferred aspect, the invention relates to the partially dechlorinated reactive derivatives of the aldehydes of furan and its homologues as well as to the methods for preparing said products.

An object of the present invention is to provide partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings which can advantageously be used in lieu of the aforesaid saturated halogenation products.

A further object is to provide partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings which are less violently reactive than the saturated halogenated aldehydes from which they are derived.

A further object is to provide partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five V membered rings which are more reactive than the original saturated halogenated aldehydes.

A further object is to provide-partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings which are possessed of a more fluid character than the original saturated halogenated aldehydes.

A further object is to provide partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings which are of a more viscous character than the original saturated halogenated aldehydes.

A further object isto provide partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydesof the, mono hetero atomic five membered rings which are grindably hard and may be ground or pulverized.

A further object is to provide partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings which are particularly suitable for use as curing agents.

A further object is to provide partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic .five membered rings which are particularly suitable for use as vulcanizing agents for products of a rubbery nature.

A further object is to providepartially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings which-are particularly suitable for use as hardening agents for resinous products.

A further object is to provide partiallyldehalogenated reactive derivatives of the 'substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings whichare particularly useful as curing agents foruse in solution for purposes of hardening or vulcanizing resinous or rubbery products.

A further object is to provide partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five memberedrings which are suitable for use as ouring agents for-hydroxy (OH) group containing polymers to convert the same. to a substantially infusible, thermo rigid, or vulcanized rubbery state, the said polymer containing, on a weight basis, a hydroxy (OH) group content of not less than of one per cent nor more than 56.8 per cent..

A further object is to provide partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings which are suitable for use as; curing agents for partially saponified polyvinyl esters, polyvinyl alcohols, and the polyvinyl acetals.

A further object is to provide partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings which are useful as chemical intermediates,

A further object is to provide partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings which are useful in the manufacture of dyestuffs. pharmaceuticals, photographic chemicals, tanning agents, solvents, plasticizers, resins, synthetic rubber compounding ingredients, etc., etc.

The partially dehalogenated reactive derivatives of the substantially fully saturated halogenation addition products of the mono hetero atomic five membered rings are all produced by the method comprising reacting one or more of the aforesaid saturated halogenated aldehydes under conditions calculated to achieve a partial dehalogenation.

The partially dehalogenated reactive derivatives referred to in the present invention permit of ready distinction and characterization in that, 1) they are all derived from the saturated halogenation products of the mono hetero atomic five membered rings, (2) they all contain more than 25 per cent and less than 100 per cent of the halide atoms contained in the saturated halogenated aldehydes from which they are derived, and (3) they all enter into reaction with substances such as tetraethylene pentamine upon heating, not infrequently with violence.

In its simplest aspect the products of the present invention are produced either by simply subjecting the substantially fully saturated halogenation addition products of the mono hetero atomic five membered rings to the action of heat or to the action of any one of innumerable reagents. Representative of suitable agents for reaction with the aforementioned saturated halogenated products are the following: water; ammonia and all manner of ammonia derivatives; alkali metals, oxides and hydroxides; alkaline earth metals, oxides and hydroxides; heavy metals, as well as their oxides and hydroxides in the active state; carbonates, sulphides, sulphites, borates, the salts of weak inorganic acids, as well as the salts of virtually all organic acids; and organic compounds of all sorts, virtually without qualification. The objective of any reaction is to achieve the partial dehalogenation.

In reacting the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings the only requisite is that the reaction conditions as regards pressure, temperature, time, etc., as well as the chemical co-reagent, if any, be such that the dehalogenation shall not be carried beyond the point where more than '75 percent of the halogenated aldehydes original halide content is removed. When more than three-quarters of the original halogen content is removed in the I process of dehalogenation, then the resultant reaction products may be characterized as falling outside of the scope of reactivity with which the herein described products are possessed. The dehalogenated products which retain less than 25 per cent of the original halogenated aldehydes halogen content are either but slightly reactive or non-reactive. These products are extremely useful for a wide variety of purposes, but they do not take the place of the reactive products of the present invention.

The substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings as well as the methods of preparing the same are fully described '4 in copending application, Serial No. 464,524, filed November 4, 1942.

Briefly and generically described, the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings are produced by the method which comprises the steps of diluting a mole of one or more of the said aldehydes with at least a mole of solvent, and then rapidly introducing halogen in the proportion of substantially four atoms of halogen per molecule of the said aldehyde while maintaining the temperature below the point of spontaneous decomposition. A more specific procedure is shown by the method of chlorinating furfural, which comprises the steps of diluting a mole of said aldehyde with at least a mole of solvent and then rapidly introducing chlorine in the proportion of substantially four atoms of chlorine per molecule of the said aldehyde, while maintaining the temperature below the point of spontaneous decomposition.

Of the known aldehydes of the mono hetero atomic five membered rings furfural is by far the most abundant and, indeed, because of its agricultural origin, may be said to be inexhaustible. For this reason the present inventors, in the majority of the ensuing illustrative examples, list as the specific progenitor the halogenation product of furfural. It should be clearly understood, however, that the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings other than furfural are usable.

Chlorine is by far the most abundant, most available, and most widely distributed halogen element in the earths crust. For this reason, in most of the ensuing examples, the present inventors have, for purposes of illustration, listed the chlorinated aldehydes in preference to the other halogenated aldehydes. It is to be distinctly understood, however, that the halogenation products other than those of chlorine, that is fluorine, bromine, and iodine, are also usable in the present invention.

As has already been indicated the partially deavailable mono hetero atomic five membered ring aldehyde is furfural, while chlorine is by far the most practical halogen. For these reasons, then, the saturated chlorination product of furfural is shown as the specific reactant in many of the following illustrative examples in which the quantities are stated in parts by weight.

As has already been indicated, the partially dehalogenated reactive derivatives of the present invention can be prepared by subjecting to suitable heat treatment, the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings. A more specific embodiment consists in subjecting the substantially fully saturated chlorination addition product of furfural to the action of heat either per se or in the presence of a substantially inert diluent. (It is to be understood that under appropriate conditions of reaction virtually all manner of so-called substantially inert diluents can be made to react, e. g., in the presence of substances as anhydrous aluminum chloride, etc.)

Example I Chlorinated furfural (chlorine content 59%), 47.6 parts, is heated to a temperature of approximately 370 F. under a pressure of from to 300 mm. of Hg. The rate of heating may be so regulated that the processing is completed in approximately two to three hours; and the final weight of residuum should be between 41 and 42 parts. The above product is decidedly more fluid than the original chlorinated furfural and is possessed of a chlorine content of 55.07 per cent.

Example II Chlorinated furfural, 47.6 parts, is subjected to the action of heat under a pressure of. from 100 to 300 mm. of Hg at a maximum temperature of 400 F. The reaction may be completed in approximately four hours sothat one ends up with between 35 and 36 parts of partially dehalogenatedreactive material.

Example III Chlorinated furfural, 47.6 parts, is subjected to the action of heat under a pressure of from 100 to 300 mm. of Hg at a maximum temperature of 400- F. The reaction may be completed in approximately four hours so that one ends up with between 28.5 and 29.5 parts of partiall dehalogenated reactive material.

Example IV Chlorinated furfural, 47.6 parts, is subjected to the action of heat under a pressure of from 100 to 300 mm. of Hg, and finally under a pressure of less than 20 mm. of Hg. The maximum temperature may be in the neighborhood of 390 F. and the operation may be completed in five and one-half hours so that one ends up with a residuum of 23.3 to 24.3 parts.

It will be noted that in each of the above four examples chlorinated furfural was subjected to a heat treatment which was varied in severity. It is also possible to carry out the heat treatment under conditions of super-atmospheric pressure or at atmospheric pressure or at pressures lower than those indicated, and for each condition, it is possible to procure partially dehalogenated reactive derivatives.

Example V A mixture comprising 47.6 parts of chlorinated furfural and 47.6 parts of xylene is refluxed for a period of five hours, The mixture is then partially distilled. first under a pressure of from 100 to 300 mm. of Hg, and thenunder a pressure of less than 20 mm. of Hg. The temperature may advantageously be kept at 325 F. and the heat is maintained until the rate of distillation appreciably slows up and the weight of residuum falls within the range of approximately 35 to 38 parts. This dehalogenated reactive derivative contained 56.5 per cent of chlorine, possessed an acid number of 126, a saponification number of 173, a mean molecular weight of approximately 450, and a specific gravity of 1.619.

Example VI A mixture comprising 47.6 parts of chlorinated furfural and. 23.8 parts of xylene is refluxed for approximately three hours, and then subjected to partial distillation, first under a pressure of between 100' and 300 mm. of Hg and then under a pressure of less than 20mm. of Hg, while maintaining a temperature of approximately 325 F. The processing is continued until the rate of distillation drops down and the weight of residuum falls within the range of from 34 to 35 parts. This product analyzed 55.72 per cent of chlorine.

Example VII Amixture comprising 47.6 parts of chlorinated furfural and, 11.9,parts of ,xyleneis refiuxedgfor 6. approximately-three hours and then subjected to partial distillation, first under a pressure of from to 300 mm. of Hg and then under a pressure of less than 20 mm.of Hg. Approximately 36 to 37 parts of residuum are procured.

Example VIII A mixture comprising 47.6 parts of chlorinated furfural and 47.6 parts of xylene is refluxed for a period of approximately five hours and is then subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg. The heating is continued until a residuum weighing between 20 and 21 parts and containing approximately 51.25 per cent of chlorine is obtained.

The four examples immediately preceding illustrate the partial dechlorination of chlorinated furfural in the presence of a substantially inert solvent. Countless other solvents or diluents may be employed including aliphatic hydrocarbons, aromatic hydrocarbons. chlorinated hydrocarbons, etc. There isevidence that in almost every case the so-called substantially inert'solvent or diluent is slightly attacked. It has also been found that if appropriate catalysts such as anhydrous aluminum chloride be added to the reaction, very profound reactions may occur between the solvent and the chlorinated furfural.

Example IX A mixture comprising 52.5 parts of chlorinated furfural and 96.0 parts of methanol is refluxed for a period of about ten hours when a loss in weight of approximately 18.0 parts will occur. The loss in weight is almost exclusively due to evolved methyl chloride. The mixture is then subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and then under a pressure of less than 20 mm. of Hg, when a yield of approximately 45.5 parts of a partially dehalogenated reactive derivative results. This product analyzed carbon 36.67 per cent, hydrogen 3.99 per cent. chlorine 31.22 per cent, oxygen 28.1 per cent, acid number 21.05, saponification number 744, specific gravity 1.414 and methoxy group content 21.45 per cent.

Example .X

Example XI A mixture comprising 47.56 parts of chlorinated furfural and 16.04 parts of methanol is refluxed until an initial loss in weight of approximately 5.1 parts occurs. The mixture is then subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg to yield approximately 42.4 parts of a partially dehalogenated reactive derivative containing 42.0 per cent of chlorine and 14.13 per cent of methoxy.

Example XII Amixture comprising 47.56 parts of chlorinated furfural and.8. 02 parts of methanol is refluxed until an initial loss in weight of approximately 5.1 parts occurs. The mixture is then subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and finally under 2. pressure of less than 20 mm. of Hg to yield approximately 41.8 parts of a partially dehalogenated reactive derivative containing 43.0 per cent of chlorine and 12.06 per cent of methoxy.

Example XIII A mixture comprising 47.56 parts of chlorinated furfural and 8.02 parts of methanol without any preliminary reflux is immediately subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg to yield approximately 44.85 parts of a partially dehalogenated reactive derivative containing 48.5 per cent of chlorine and 8.76 per cent of methoxy,

Example XIV A mixture comprising 47.56 parts of chlorinated furfural and 16.04 parts of methanol without any preliminary reflux is immediately subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg to yield approximately 42.0 parts of a partially dehalogenated reactive derivative containing 44.3 per cent of chlorine and 12.12 per cent of methoxy.

Example XV A mixture comprising 47.56 parts of chlorinated furfural, 64.08 parts of methanol, and 1.8 parts of water is refluxed until an initial loss in weight of approximately 5.1 parts occurs. The mixture is then subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg to yield 41.6 parts of a partially dehalogenated reactive derivative containing 37.07 per cent of chlorine and 16.01 per cent of methoxy.

Example XVI A mixture comprising 47.56 parts of chlorinated furfural, 32.08 parts of methanol, and 3.6 parts of water is refluxed until an initial loss in weight of approximately 5.1 parts occurs. The mixture is then subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg. to yield 38.55 parts of a partially dehalogenated reactive derivative containing 38.0 per cent of chlorine and 11.8 per cent of methoxy.

Example XVII A mixture comprising 47.6 parts of chlorinated furfural, 16.04 parts of methanol, and 1.8 parts of water without any preliminary reflux is immediately subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and then under a pressure of less than 20 mm. of Hg to yield 41.6 parts of a partially dehalogenated reactive derivative containing 44.07 per cent of chlorine and 9.05 per cent of methoxy.

Example XVIII Calcium carbonate, 5.0 parts, is slowly added to a solution comprising 47.6 parts of chlorinated furfural dissolved in 70.0 parts or methanol. The mixture is then heated and kept hot for a short period of time and is then concentrated under a pressure of from 100 to 300 mm. of Hg to a weight of approximately 70.5 parts. The further processing is optional, but the following gives good results: To the concentrate add 60.0 parts of benzene, and 32.0 parts of water. Shake, separate the layers, dry the benzene layer, filter and, if desired, clarify with decolorizing carbon. The benzene solution is then subjected to partial distillation, first under a pressure of from to 300 mm. of Hg and then under a pressure of less than 20 mm. of Hg to yield approximately 40.9 parts of an amber colored partially dehalogenated reactive derivative containing 40.47 per cent of chlorine and 16.44 per cent of methoxy.

Example XIX Twenty parts of calcium carbonate (powdered marble flour) is slowly added to a solution comprising 47 .6 parts of chlorinated furfural dissolved in 70.0 parts of methanol. After heating for a short period with continued agitation the mixture is subjected to slow vacuum concentration under a pressure of from 100 to 300 mm. of Hg. The concentrate may, from this point on, be processed as follows: Add benzene and water, agitate, let stratify, decant the benzene layer, dry the latter and, if desired, clarify with decolorizing carbon and then distill ofi the benzene, preferably under reduced pressure at a temperature below 250 F. Approximately 37.0 parts of a light amber colored partially dehalogenated reactive derivative containing 39.25 per cent of chlorine and 20.1 per cent of methoxy is obtained.

Example XX Zinc dust, 3.27 parts, was slowly added to a mixture consisting of 47.6 parts of chlorinated furfural and 32.08 parts of methanol. The mixture was cooled down to prevent excessive loss through volatization. The mixture was subjected to partial distillation under a pressure of from 100 to 300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg to yield 31.1 parts of a partially dehalogenated reactive derivative which contained 24.5 per cent of chlorine and 4.28 per cent of methoxy. The above weight and percentage data includes the zinc chloride synthetically formed.

Example XXI Zinc dust, 0.327 part, was slowly added to a mixture consisting of 47 .6 parts of chlorinated furfural and 16.0 parts of methanol.The mixture was subjected to partial distillation, first under a pressure of between 100 and 300 mm. of Hg and then under a pressure of less than 20 mm. of Hg to yield 29.7 parts of a partially dechlorinated reactive derivative containing approximately 25.8 per cent of chlorine and 5.89 per cent of methoxy. Zinc dust and zinc salts, e. g., zinc chloride function as catalysts resulting in a vigorous reaction accompanied by a copious evolution of methyl chloride.

Example XXII Zinc chloride, 0.68 part, was added to a mixture consisting of 47.6 parts of chlorinated furfural and 16.04 parts of methanol. The mixture was subjected to partial distillation, first under a pressure of between 100 and 800 mm. of Hg and then under a pressure of less than 20 mm. of Hg to yield 30.8 parts of a partially dehalogenated reactive derivative which contained 30.4 per cent of chlorine and 7.86 per cent of methoxy. The product of this reaction was a grindably hard mass.

Example XXIII Zinc chloride, 0.68 part, was added to a mixture consisting of 47 .6 parts of chlorinated furfural and 2,475,801" 9 1o 7 32.08 parts of methanol; The mixture wasrelatter was then dried, deoolorized', filtered and fiuxed for four hours and then subjected to partial then subjected to partial distillation, first under. distillation, first underapressure of from 100 to". a pressure of between 100 and 300 mm. of H3 300 mm. of ,Hg andfinally under a pressureof. and finally under a pressure'of less than 20 mm. less than 20 mm.-of Hg to yield a grindably hard 5 of Hg to yield 35.5 parts of apartiallydehalogensolid product weighing 24.8 parts. This partially ated reactive ethoxy'oontaini'ng derivative which. dechlorinated reactive derivative contained 22.4 analyzed carbon.40.0 'per cent, hydrogen 4.29 .per per cent of chlorine and 3.87 percent of methoxy. cent, chlorine 32.0 per cent and ethoxy 15.2 per It is interesting to note that when catalysts such cent.

as powdered zinc or'zinc salts are employed, the Example XX V III' resultant compounds are possessed, m Chlorinated fur'fur'a l, 143 parts, was dissolved lower ether or methoxy content than m the in 49.0'pa'rts of normal butanol and the resultant sence'of such a catalyst. mixture was then subjected to slow distillation;

Erample'XXIV first under a press'ure of'betw'een 100] and 300 f H and 'finall under'a' ressure f less' A solution comprising 4.1 parts of anhydrous i g 1 0 Swim acetate dissflved in 32-08 parts vv ii ailifi yie 'ii gfiifieit iii' h I i 7 l met anol was added to 4'7 6 parts of chlorinated bun, 107 per cent hydrogen, 16.1 per cent ch1o furfur-al. The mixture was then subjected to d 8 partial distillation, first under a pressure of bean 5 per mm 33 tween 100 and 300 mm.' of Hg and then under E'xa'mpleXXIX A of furfural and 63.25 parts of normal butyl alcohol sixty parts benzene 'and'sez Paris Water was refluxed for four hours and'th'e'n subjected to were added to the reslduum and after 25 distillation at atmospheric'pressure. Fresh q'uan agitation, the stratified layers were l' tities of butanolwere introduced to replace that The benzene layer was dned P which distilled off. The mixture was then suband filtered and the benzene was then dlstllled jettedto an additional refluxing for four hours" er reduced presiure'm i and then subjected to' partial distillation, first a partially dehalogenated react1ve derivat ve under a pressure of from 100 to 300 of gvlgnch contaizied 44.6175 ent chlorme i and finally under a pressure ofless than 20 mm.

. 6 per cen of me oxy besides some ace a of Hgfltg Wadi-2:82 parts of axparfianyvdechlm groups rinatedreactivederivative which analyzed 57.3 stamp e per cent carbon, 7.25 per cent hydrogen, 9.32 per .A solution comprising 11.2 parts of potassium cent chlorine, and 26.14 per cent o ygen. hydroxide dissolved in 60.0 parts of methanol was Example slowly added to a mixture consisting of 47.6 parts of chlorinated ,furfural dissolved in 20.0 parts of methanol. The mixture was subjected to partial, 40, distillation, first under a pressure of between 100 and 300 mm. of Hg and-then under a pressure of less than 20 mm. of H g. Sixty parts of benzene and 36.0 parts of water were then added to the residuum and-the resultant mixture after shaking, was permitted to stratify and the benzene layer was removed, dried; 'deoolorized, and finally A mixture comprising 10.9 parts of chlorinated furfural and 46.0 parts ofiso-bu'tanol was subjected, first to slow "fractional distillation at atmospheric pressure and then to partial distilla tion first under a pressure of 100 to "300 mm. of Hg and 'finallyundena pressure of less than 20: mm.'of Hg to yield 11.16 "parts of a reactive derivative'which'analyzdcarbon 55.45per cent, hy droge'n'7.62 per centaii'd chlorine 13.91 per cent.

freed from the benzene by vacuum 'c0ncentrati0n." Example X X XI Approximately 36.0 parts of'a partially dechlo H rinate'd reactive derivative were "procured. x u m 1 F ;4 9f h fF? furfural and 37.06 parts of iso-butanol without Example X any preliminary refluxingfwas imm'ediately'subjected to partial distillation, first under a pres sure of between 100 and 300mm. of Hg and finally under a pressure of less than 20 mm. of

A mixture comprising 15,.0 parts of chlorinated furfural and 39.5 parts of anhydrous ethanol was refluxed for a period of approximately thirty- I I v v P three hours. A large quantity of ethyl chloride Hg t0 y d 45.66 parts of a reactive derivative was evolved. The mixture was then subjected'to Which contained 37-8 per cent of chlorine.

partial distillation, first under a pressure of from m i 'XXXH 100 to 300 mm. of Hg and then under a pressure d d I V I, I v v d of less than 20 mm. of Hg to yield 11.6 parts of A mlxture comprlsme 4-0 Par,ts of @hlormated a partially dehalogenated reactive ethoxy confurfuml and 9- parts of a Secondary butyl taining derivative which analyzed carbon 45.15 cohol Was Subjectedfirst to Slow fractional tillation at atmospheric pressure and then to per cent, hydrogen 5.04 per cent, chlorine 20.35 per cent, oxygen 28.45 per cent and ethoxy 26.55 dlrect partlal t l e a first under a pressure per cent of between 100 and 300 mm. of Hg and finally Example-XXVI] under a pressure of less than 20 mm. of Hg to n yield 11.11 parts 'ofa reactive derivative which calcumt carbonate fl was Slowly analyzed 52.5 'per cent carbon, 6.1 per cent hy-' troduced into a mixture consisting of 47.6 parts drogem and 172 per cent chlorine v of chlorinated furfural and 100.15parts of an- ,5 i hydrous ethanol. The mixture was concentrated Example X- 7 under a pressure of between 100 and 300 mm. of A'mixture comprising 4.76 arts of chlorinated Hg so as to yield 83.0 parts of residuum. Then furfural and 5.92 parts of tertiary butyl alcohol. 36.0 parts of water and 60.0 parts of benzene were was subjected to slow fractional distillation at added,'the mixture agitated, the layers permitted atmospheric pressure. Very considerable quanto stratify, and the organic'layer removed. The titiesof gas were evolved. Themixture was then subjected to direct distillation at atmospheric furfural and 18.02 parts of the mono ethyl ether pressure and finally under a pressure of less than of ethylene glycol was directly subjected to partial 20 mm. of Hg to obtain 9.09 parts of derivative. distillation under a pressure of less than 20 mm. Tertiary alcohols of all sorts are more or less comof Hg to yield 45.64 parts of a reactive derivative pletely decomposed by the saturated halogenwhose alkoxy content was 10.24 per cent, calcuation products of the aldehydes of the mono lated as ethoxy.

hetero atomic five membered rings. Example XXXXI Example XXXIV A mixture comprising 47.6 parts of chlorinated A mixture comprising 13.0 parts of chlorinated furfural and 58.08 parts of butyl acetate was first furfural and 65.5 parts of secondary amyl alcohol refluxed four hours and then subjected to partial is refluxed for a period of about twelve hours, and distillation, first under a pressure of between 100 then subjected to fractional distillation at atmosand 300 mm. of Hg and finally under a pressure pheric pressure, then to direct distillation under of less than 20 mm. of Hg to yield 442 parts of a reduced pressure, first under a moderate vacuum reactive derivative which contained 47.8 per cent and finally under a pressure of less than mm. of chlorine.

of Hg. A reactive derivative, 10.07 parts, is procured which analyzed carbon 52.0 per cent, hy- Exafiple XXXXH I drogen 5.69 per cent and chlorine 7.07 per cent. A mixture comprising 47.6 parts of chlorinated Example XXXV 20 furfural and 31.02 parts of ethylene glycol was directly subjected to partial distillation under a A mixture comprising 47.6 parts of chlorinated pressure of less than 20 mm. of Hg to yield 44.1

furfural and 27.6 parts of secondary amyl alcohol parts of a partially dehalogenated derivative W t ou y preliminary refluxing is immediately which contained 31.33 per cent of chlorine. subjected to partial distillation, first under a pressure of between 100 and 300 mm. of Hg and 20 i t XXXXHI then under a pressure of less than 20 mm. of Hg A mixture eompl'lslng Parts Of t d to yield 41.27 parts of a partially dehalogenated furfural and 40.0 parts of ethylene chl r y n reactive derivativ which contained 4085 per is directly subjected to partial distillation under cent of hlori a pressure of less than 20 mm. of Hg to yield 44.4 parts of a reactive derivative which contained Example XXXVI 50.05 per cent of chlorine. A mixture comprising 47.6 parts of chlorinated furfural and 27.6 parts of secondary amyl alcohol Example XXXXIV is directly subjected to distillation under a pres- A mixture comprising 47.6 parts of chlorinated sure of less than 20 mm. of Hg to yield 39.83 parts furfural and parts of acetone (dimethyl of a reactive derivative containing 41.7 per cent ketone) was refluxed four hours and then subof chlorine, jected to partial distillation, first under a pres- Erample XXXVII sure of from 100 to 300 mm. of Hg and finally A mixture comprising 12.0 parts of chlorinated g g fi g of less t of to furfural and 35.0 parts of tetrahydro furfuryl .3716 51 par s We denva We contain" alcohol is subjected to slow distillation at atmosmg per can 0 0 pheric pressure-and then to partial distillation, Example XXXXV first under a pressure of from 100 to 300 of A mixture comprising 47.6 parts of chlorinated Hg and then 111 1der a PreSWre of less than 20 furfural and 36.05 parts of ethyl methyl ketone of Hg t0 yleld apPmxlmijltely P of was refluxed for two hours and then subjected to a sllghtly rubbery reactlve reslduum Whlch partial distillation, first under a pressure of from tained about 11.32 per cent of chlorine. If the 100 to 300 mm. of Hg and then under a pressure heating be continued, a more rubbery product is of less than 20 mm. of H to ield 41.0 rt f procured and if the heating be still further cong y pa 5 o a partially dechlorinated reactive derivative continued, a substantially mfusible hard rubbery taming 5L9 per cent of chlorine material results.

E m l 1 Example XXXVIII Ia P e XXXXV A mixture comprising 47.6 parts of chlorinated Amixture comprising 10.5 parts of chlorinated furfural and Mimi parts of di isobutylene was furfural and parts of benzy} w first refluxed for a period of four hours and then heated and then subjected to partial distillation, Subjected to partial distillation, first under a pres first under a pressure of between 100 and 300 mm. sure of from 100 to 300 mm. of Hg and finally of Hg and finally under a pressure of less than under a pressure of less than 20 mm of Hg to 20 of The r rubbery. partlany 60 yield 39.7 parts of a reactive derivative containdehalogenated reactive residuum contained 15.92 mg 3&6 per cent of chlorine per cent of chlorine.

Example XXXXVII A mixture comprising 47.6 parts of chlorinated furfural, 23.8 parts of xylene, and 16.04 parts of methanol was refluxed for three hours and then subjected to partial distillation under a pressure of less than 20 mm. of Hg to yield 26.36 parts of a reactive derivative containing 46.2 per cent of enated reactive derivative which contained 37.22 chlorine and 419 per cent of methoxy.

er cent of chlorine and had an alkoxy content quivalent to 7.48 per cent calculated as methoxy. Example XXXXVHI A mixture comprising 47 .6 parts of chlorinated Example XXXX furfural, 32.0 parts of butanol, and 0.68 part of A mixture comprising 47.6 parts of chlorinated anhydrous zinc chloride was refluxed for. four Example XXXIX A mixture comprising 47.6 parts of chlorinated 65 furfural and 38.03 parts of the mono methyl ether of ethylene glycol was directly subjected to partial distillation under a pressure of less than 20 mm. of Hg to yield 43.52 parts of a partially dehalo- 13 hours and then subjected to partial distillation, first under a pressure of between 100 and 300 mm. of Hg and then under a pressure of less than 20 mm. of Hg to yield 23.39 parts of a grindably hard reactive derivative containing 14.91 per cent of chlorine.

Example XXXXIX A mixture comprising 24.0 \parts of chlorinated funfural, 36.0 parts of mono methyl ether of ethylene glycol and 2.0 parts of distilled water was refluxed for eight hours and then subjected to distillation, first at atmospheric pressure, then under a pressure of between 100 and 300 mm. of Hg and then under a pressure of less than 20 mm. of Hg, ending up with a kettle jacket temperature of approximately 425 F. and continuing the reaction until the product acquired a rubbery character. A yield of approximately 11.0 parts of a black rubbery product was procured. The material analyzed chlorine 5.3 per cent, hydrogen 5.6 per cent and carbon 52.2 per cent. This particular derivative was still perspectively reactive. Had the heating and distillation been stopped earlier a more fluid and more reactive product would have been procured and vice versa, had the heating and vacuum distillation been continued beyond the point to which it was carried, then substantially infusible, rubbery, and hard products are obtained which test substantially nonreactive. When chlorinated furfural or its equivalent is reacted with the mono methyl or mono ethyl ether OLf ethylene glycol a very large quantity of alkyl halide is generated.

Example L A mixture comprising 2.38 parts of chlorinated furfural and 3.6 parts of butyl aldehyde is refluxed for four hours and then subjected to partial distillation first at atmospheric pressure and then under a pressure of less than 20mm. of Hg until at a temperature of 300 F. nothing further distills oil. A yield of 3.36 parts is procured which analyzed 70.7 per cent'orf carbon, 8.38 per cent of hydrogen, and 7.56 :per cent of chlorine.

Example LI A mixture comprising 2.38 parts of chlorinated turfural, 4.64 parts of the methyl ester of alphamethoxy isobutyric acid was refluxed for three hours and then subjected to partial distillation under a pressure of less than 20 mm. of Hg at a temperature of 340 F. to yield 1.26 parts of a reactive product.

Example LII Anhydrous aluminum chloride, 2.67 parts, is cautiously added to a mixture comprising 4.2 parts of chlorinated iunfural and 4.7 parts of benzene. The mixture was then refluxedupon a water bath for about two hours and then 20.0 parts of water and 8.0- parts of benzene were added along with a little hydrochloric acid and the mixture was refluxed for thirty minutes. The mixture was then permitted to cool, the layers separated, and the benzene solution was decolor- 'ized, filtered, and then concentrated by evaporation at a temperature of 212 F. at a pressure of less than 20 mm. of Hg. A more or less reactive hard product weighing 5.67 parts was procured.

Ewample LIII Anhydrous aluminum chloride, 2.67 parts was slowly added to a mixture comprising 4.2 parts of chlorinated 'furfuraland'-1'2.4.- parts of benzene.

The mixture-was kept co'olrfor a period of one hour and the temperature wasthen permitted to come up to that of the room and finally it was subjected to refluxing for about one-half hour, then cooled somewhat. Water,-benzene and a little hydrochloric acid were added and the mixture subjected to a short reflux, cooled, the layers separated (which latter operation was expedited through the addition of further quantities of hydrochloric acidlfiltered, and evaporated ofithe solvents under a pressure or less'than 20 mmpof Hg so that 4.87 parts of a derivative were procured which analyzed carb'on'72.1 per cent, hydrogen 4.81 per cent and chlorine 13.77 per cent.

Example LIV Anhydrous aluminum chloride, 2.67 parts, was

added to a. mixture consisting of 4.2 parts of chlorinated funfural and 20.23-parts of di-isobutylene. After the aluminum chloride had been added the mixture was permitted .to cool somewhat and 1.0 part of hydrochloric acid along with 20.0 parts of water were added. The mixture Was refluxed thirty minutes. After cooling the layers were separated. The organic layer was filtered and the .benzene' and excess di-isobutylene, etc., were distilled on, yielding 7.61 parts as the derivative.

Example LV A mixture comprising 4.5 parts of chlorinated iurfural and 3.1 parts of a terpineol was heated upon a water bath for one hour. The temperature was then raised to'300F-. under a pressure of between 100 and 300mm. of Hg and then to 350 F. under the same pressure until a grindably hard product weighing 4.29 parts was procured.

Example LVI Live steam was passed into a mixture comprising 8.0 parts of chlorinated ifurfuraland 15.0 parts of xylene. The steam was: passed in for a period of approximately six and one-half hours and the mixture was then subjected to partial distillation, first under a pressure of 100 to 300 mm. of Hg and then under a pressure ofless than 20 mm. of Hg ending up with a yield of 3.75 parts of derivative.

Ezrample LVII and the evolved gases "were collected, then switched to partial distillation, flrstunder a pressure of 100 to 300mm. of Hg and then under a pressure of less than 20 mm. of Hg endingup with a reactive chlorinec'ontainlng residuum of 1.32 parts. The 'niaterial was black in color, grlndably hardgand had a'rather high melting pom Example LIX A mixture comprising 4.0 parts of chlorinated dehyde was refiuxed for eight hours and then after separating the layers, the organic layer was distilled under a pressure of from 100 to 300 mm. of Hg to yield 2.56 parts of a moderately hard, solid material possessed of a fair reactivity.

Example LX A mixture comprising 12.0 parts of chlorinated furfural and 24.0 parts of aqueous solution containing 40% formaldehyde was refluxed for seven hours and then distilled, first at atmospheric pressure and then under a pressure of between 100 and 300 mm. of Hg. The heating was continued until, at a temperature of approximately 300 F., a grindably hard resinous product weighing 8.70 parts was procured. The material had a capillary tube melting point of approximately 121 F. and analyzed 12.14 per cent chlorine. The product reacted readily with various reagents.

Emample LXI A mixture comprising 16.0 parts of chlorinated furfural and 32.0 parts of aqueous formaldehyde solution, which latter containing 40% of formaldehyde, was refiuxed for fifteen hours while the evolved gases were collected. The pressure was then reduced between 100 and 300 mm. of Hg and the mixture was subjected to partial distillation, ending up with a temperature of approximately 300 and a grindably hard resinous mass weighing 11.81 parts which analyzed 10.63 per cent chlorine.

Example LXII A mixture comprising 4.0 parts of chlorinated furfural and 4.0 partsof cotton seed oil was heated to 300 F. for thirty minutes, then at 325 F. for two hours, and finally at 350 F. for about two hours. Considerable quantities of gaseous product (HCl) were evolved. If the mixture be heated for a further period of time then the product passes over into a rubbery composition. Material of this sort by being subjected to temperature in excess of 350 F. for a period of two or more hours can be converted into a material suitable for the manufacture of friction elements and brake blocks.

Example LXIII A mixture comprising 8.0 parts of chlorinated furfural and 24.0 parts of water was refluxed for a period of one hour. The material was in two layers, one in an aqueous phase and the other in an organic phase. The mixture was then subjected to partial distillation under a pressure of 100 to 300 mm. of Hg yielding 3.68 parts of derivative analyzing 26.45 per cent chlorine.

Example LXI V A mixture comprising 6.0 parts of chlorinated furfural and 8.0 parts of raw linseed oil was heated to a temperature of 350 F. and held there until it gelled. A gelatinous product weighing 12.07 parts was procured. During the reaction considerable quantities of HCl were evolved.

Example LX V A mixture comprising 6.0 parts of chlorinated furfural and 8.0 parts of palm oil fatty acid was heated to 350 F. This temperature was maintained until the product gelled (one hour). Considerable quantities of hydrogen chloride were evolved and the yield of derivative was 11.67 parts. In a somewhat analogous manner all types of vegetableand animal oils, fats, waxes and 16 their fatt acids may be reacted including rosin, turpentine, and all manner of related products.

Example LXVI A solution consisting of 4.76 parts of chlorinated furfural dissolved in 7.0 parts of methanol was added to a solution comprising 6.56 parts of anhydrous sodium acetate dissolved in 35.0 parts of methanol. The mixture was then refluxed for one hour and let cool. The product was suction-filtered, the filtrate being washed with an additional quantity of methanol. The filtrate was then subjected to partial evaporation, first at atmospheric pressure and then under a pressure of from to 300 mm. of Hg. A residuum of 9.0 parts resulted. This latter was then extracted with anhydrous ethyl acetate, filtered and reconcentrated so as to evaporate off the ethyl acetate. The residuum which comprised the main reaction product weighed 4.0 parts and had a chlorine content of approximately 10 per cent.

Example LXVII Anhydrous aluminum chloride, 2.67 parts, was added to a mixture comprising 4.2 parts of chlorinated furfural and 19.39 parts of mono chloro benzene. Approximately one and one-half hours was utilized in introducing the aluminum chloride at the end of which time the mixture was kept cool for an additional thirty minutes, and thereafter, it was refluxed for a period of one hour. The mixture was then cooled to F. and 1.0 part of concentrated hydrochloric acid and 20.0 parts of water were added. The material was refiuxed for thirty minutes, the layers separated, the organic layer filtered and the latter then subjected to partial distillation under a pressure of from 100 to 300 mm. of Hg until at an end temperature of 400 F. nothing further distilled over. A yield of 8.33 parts of a highly viscous material resulted.

Example LX VIII A mixture comprising 9.52 parts of chlorinated furfural and 1.84 parts of glycerine is heated to 212 F. for a period of two hours, then at 275 F. for a period of one hour, then at 300 F. for a period of one hour, and finally at 300 F. for a period of one hour under a pressure of from 100 to 300 mm. of Hg. Approximately 7.6 parts of a partially dechlorinated reactive derivative resulted. The quantity of glycerine employed may be varied between rather wide limits and a timetemperature schedule other than that indicated may be used. Utilizing 9.52 parts of chlorinated furfural and the indicated time-temperature schedule, the following yields of reactive products result, when one utilizes the following respective quantities of glycerine: Parts glycerine 1.23, 1.84, 2.0, 2.5, 3.0, 3.68, 4.0, 4.5, 5.52; the yield of reactive product equals 7.26, 7.6, 7.7, 7.84, 8.39, 9.10, 9.25, 9.55 and 10.57 parts respectively. Reactive products such as the above are capable of curing or setting up such products as sugar, dextrose, corn sugar, formal sugars, caramel, acetone-formaldehyde reaction products, etc.

Example LXIX A mixture comprising 9.52 parts of chlorinated furfural and 3.68 parts of caramel (prepared from sucrose) was heated first at 212 F. and then at a higher temperature of 250 F. The ultimate material was possessed of a high melting point 17 and with slightly more heating, passes over into an infusible product.

Example LXX A mixture comprising 9.52 parts of chlorinated furfural and 3.68 parts of sorbitol was heated first at 212 F., then at 250 F., then at 275 F., and finally for two hours at 300 F. A yield of 8.10 parts of reactive product resulted.

Example LXXI Butadiene is passed into 4.214 parts of chlorinated furfural dissolved in 5.786 parts of carbon tetrachloride. The mixture is kept under conditions of reflux and the gas is passed in for a period of eight or more hours. The bulk of the carbon tetrachloride is then distilled oil under atmospheric pressure and finally the temperature is stepped up to 212 F. with a reduction in pressure to between 100 to 300 mm. of Hg. Approximately 4.41 parts of a reactive product result.

Example LXXII Five and sixty-five hundredths parts of a solution containing 2.38 parts of chlorinated furfural dissolved in carbon tetrachloride is added to 13.6 parts of a solution comprising 1.36 parts of natural rubber dissolved in benzene. The mixture is stirred and refluxed for a period of one hour and is then concentrated until the residuum weighs approximately 8.5 parts. The mixture is then further refluxed for an hour and is then subjected to partial distillation at atmospheric pressure when 3.43 parts of a semi-stifi rubbery mass is procured. This latter is then extracted with methanol so as to remove unreacted chlorinated furfural, etc. We end up with 2.25 parts of a product of moderate reactivity which contains 18.45 per cent of chlorine.

Example LXXIII A mixture comprising 47.6 parts of chlorinated furfural and 1.8 parts of water without any preliminary refluxing is directly subjected to partial distillation under a pressure of from 100 to 300 mm. of Hg until approximately 41.6 parts of a reactive derivative containing about 53 per cent of chlorine is obtained as the residuum. It was noted that when the indicated quantity of water was used, the reaction or dehalogenation proceeded at approximately twice the rate at which reaction occurs under similar conditions but in the absence of water.

Example LXXI V A solution comprising 12.14 parts of 28 per cent aqueous ammonia dissolved in 12.14 parts of methanol is slowly added to a solution of 47.6 parts of chlorinated furfural dissolved in 47.6 parts of methanol. The mixture is concentrated under a pressure of from 100 to 300 mm. of Hg and then water and benzene are added to aid in washing out water-soluble material such as ammonium chloride. The benzene layer is separated, filtered and may, if desired, be dried and clarified with a decolorizing carbon. The benzene layer is then subjected to partial distillation to remove benzene, preferably under a pressure of from 100 to 300 mm. of Hg and then under a pressure of less than 20 mm. of Hg while maintaining the temperature preferably not above 250 F. The reresultant reactive derivative, besides containing chlorine, contains nitrogen. Considerable leeway is permissible as regards the amount of ammonia that may be utilized in these reactions. It is also possible to use more or less diluent or to use a diluent other than the indicated methanol. Finally, it should be emphasized that instead of ammonia one may utilize materials such as ammonium carbonate, ammonium acetate, ammonium sulphide, ammonium iodide, as well as any of the simpler organic amines such as the mono methyl, di methyl, or tri methyl amine or the corresponding ethyl, propyl, isopropyl, butyl, etc. amines. In this manner it is possible to procure any number of reactive derivatives which contain the element, nitrogen, as an integral part of the derivative.

Example LXX V A solution consisting of 9.3 parts of aniline dissolved in an equal weight of methanol is slowly added to a solution comprising 47.6 parts of chlorinated furfural dissolved in 47.6 parts of methanol. The mixture is concentrated under a pressure of from 100 to 300 mm. of Hg and the resultant concentrate is then washed with a mixture of benzene in water. The benzene layer is then separated, dried, clarified, and subjected to partial distillation so as to remove the benzene and other ready volatiles. The resultant dark colored product which may range in consistency anywhere from a material resembling very heavy molasses to a soft solid contains besides chlorine the element, nitrogen. Considerable leeway is permissible as regards either the quantity of aniline employed or the quantity or type of diluent used. In lieu of aniline one may employ any one of a host of other aromatic or heterocyclic amines, e. g., ortho toluidine, para toluidine, xyledenes, amines of naphthols, amines of anthraquinones, amines of phenanthracines, etc. Polyamino compounds may similarly be utilized.

Example LXX VI A solution containing 9.4 parts of phenol dissolved in an equal weight of methanol is slowly added to a mixture comprising 47.6 parts of chlorinated furfural dissolved in 47.6 parts of methanol and the whole is slowly heated and may, if desired, be refluxed for a period of one hour or so or else is directly subjected to partial distillation so as to procure a concentrate amounting to approximately parts by weight. The resultant concentrate may then be washed with a mixture of water and benzene, the benzene layer separated, dried, clarified, and subjected to partial distillation under a reduced pressure so as to remove the ready volatiles. The resultant black colored material may range in consistency from a very viscous fluid to a soft solid. It desired, the water washing step may be dispensed with and the product may be directly subjected to partial distillation, first under a pressure of from to 300 of Hg and finally under a pressure of less than 20 mm. of Hg. Considerable leeway is permissible as regards the quantity of phenol employed as well as in the matter of the quantity and type of diluent and the time-temperature schedule. Further, in lieu of phenol other phenolic materials may be utilized, e. g., cresols, xy-

lenols, naphthols, as well as various substituted phenols, e. g., tertiary amyl phenol, para chlor phenol, and para nitro phenol.

Example LXX VI I A mixture comprising 10.9 parts of para amino phenol dissolved in an equal quantity of methanol is slowly added to a mixture comprising 47.6 parts of chlorinated furfural dissolved in an equal weight of methanol. The mixture is immedi- 19 ately subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and then under a pressure of-less than 20 mm. of Hg to yield a black colored reactive residuum. If desired, the initial mixture may first be concentrated to a weight of about 75 parts and the latter then subjected'to water washing and extraction'with benzene, etc. examples, here too considerable leeway is permissible as regards the quantity of amino phenol employed, the quantity and type of diluent and in the matter of the time-temperature schedule. To the best of our knowledge any of the amino phenols may be utilized in this reaction. Amino phenols substituted with hydrocarbon, halide, or

nitro groups are also usable.

Example LXXVIII A'solution comprising 7.8 parts of sodium mono sulphide (anhydrous basis) dissolved in a mixture of aqueous methanol is added to a solution comprising 47.6 parts of chlorinated iuriural dis-- solved in an equal weight of methanol. The mixture is refluxed for a period of about one hour and is'then concentrated to a weight of about 75 parts. Water and benzene are added to the concentrate and the organic layer is then separated, dried, clarified, and subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg. The resultant reactive chlorine containmg compound also contains the element, sulphur. Appreeiable quantities of H28 are evolved.

Example LXXIX A mixture comprising 47.6 parts of chlorinated furfural', 47.6 parts of benzene and 16.7 parts of mercapto benzothiazole is subjected to direct partial distillation, first under a pressure of from 100 to'300'min. of'Hg' and finally under a pressure of less than 20 mm. of Hg. The resultant reactive chlorine containing derivative is found to contain the'element, sulphur. Considerable leeway is permissible as regards the quantity of the organic sulphur compound, the type and quantity of diluent, as well as in the matter of the time-temperature schedule. In lieu of the above indicated mercapto benzothiazole one may employ any one of thousands of'other organic compounds containing sulphur or its anologues, e. g., benzo thiazole disulphide, zinc dimethyl dithio carbamate, zinc diethyl dithio carbamate, zinc dibutyl dithio carbamate, tetramethyl thiuram disulphide, tetraethyl thiuram disulphide, selenium diethyl diurea and the cyclo hexamine derivative of mercapto benzo thiazole, 2,2'-dithio-bis-benzothiazole, thio carbanilide, salts of pentamethylenedithio carbamate, piperidinium pentamethylenedithio carbamate, diphenyl thiourea, dipentamethylene thiuram tetra sulphide, tetramethyl thiuram monosulphide, aldehyde amine thiazole, etc.

Eirample LXXX A mixture comprising 16.6 parts of potassium iodide dissolved in 1000 parts of methanol is added to a solution of 47.6 parts of chlorinated furfural dissolved in an equal weight of methanol. The mixture is refluxed for a period of three hours and is then concentrated to a weight of approximately 75 parts. Water and benzene are added. The benzene layer is separated, dried, clarified and finally subjected to partial distillation to remove'the' ready volatiles. The resultant As in the previous two thio carbamate, 2-mercapto-thiazoline, thiourea,

chlorine containing re'active derivative also contains the element, iodine. is permissible as regards the reaction conditions and in lieu of potassium iodide one may employ such materials-as ammonium iodide, casium i0- dide, rubidium iodide, sodium iodide, lithium iodide, barium iodide, strontium iodide, calcium iodide, magnesium iodide, etc. More or less elemental iodine is liberated in these reactions.

Example LXXXI A mixture comprising 11.7 parts of di-ethylamino ethanol dissolved in an equal weight of methanol is slowly added to a solution of 47.6 parts of chlorinated iurfural dissolved in an equal Weight of methanol. The mixture is refluxed for a period of three hours and is then subjected to partial distillation, first under a pressure of between 100 and 300 mm. of Hg and then under a pressure of less than 20 mm. of Hg. An optional alternative is, after the refluxing operation, to concentrate the mixture to a weight of about 75 parts and then to add water and benzene, mix thoroughly, let stratify, separate the benzene layer, dry and clarify the same and then subject to partial distillation under're'duced pressure for the purpose ofremoving the benzene and other ready volatiles. Amino alcohols, hydroxy acids, amino acids, lactones, lactides, lactanes, etc., may be used in lieu of the above di-ethylamin'o ethanol.

Example LXXXII A mixture comprising 49.0 parts of chlorinated methyl furfural and 64.0 parts' of methanol is refluxed for three hours and then subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg to yield a partially dehalogenated chlorine containing reactive derivative.

Example LXXXIII A mixture comprising 47.7 parts of chlorinated a-DYII'OIB aldehyde and 64.0'parts of methanol is refluxed for a period of three hours and then subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg to yield a partially dehalogenated chlorine and nitrogen containing derivative.

Example LXXXI V A mixture comprising 49.2 parts of chlorinated thiophen aldehyde and 64.0 parts of methanol is refluxed for three hours and then subjected to partial distillation, first under a" pressure of from 100 to 300 mm. of Hg and then under a pressure of less than 20 mm. of Hg to yield a partially dehalogenated reactive chlorine and sulphur containing derivative.

Example LXXXV A mixture comprising 83.2 parts of brominated furfural and 64.0 parts of methanol is refluxed for a period of three hours and then subjected to partial distillation, first under a pressure of from 100 to 300 mm. of'I-Ig and then under a pressure of lessthan 20 mm. of Hg to yield a partially dehalogenated reactive bromine containing derivative.

Example LXXXV-I A mixture comprising 120.8 parts of iodinated furfural and 64.0 parts of methanol is refluxed for three hours and is then subjected to partial distillation; first under a pressure of from 100 Considerable leeway to 300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg to yield a partially dehalogenated reactive iodine containing derivative. It is noted that when working with the iodine compounds appreciable amounts of elemental iodine come into being as is evidenced by the gaseous or vaporous phases possessing a violet colored hue and oftentimes iodine crystals are formed either on the sides of the reaction kettle in the condenser or in the receiver.

Ercample LXXXVII A mixture comprising 34.4 parts of the reaction product of fluorine and furfural (prepared at low temperatures in carbon ware with the fluorine electrolytically produced from hydrogen fluoride and immediately passed into the furfural which is diluted with di-chloro-di-fiuoro methane sufficiently cooled to prevent the diluent from distilling out during the halogenation) dissolved in 64.0 parts of methanol is refluxed for a period of three hours and then subjected to partial distillation, first under a pressure of from 100 to 300 mm. of Hg and finally under a pressure of less than 20 mm. of Hg to yield a reactive fluorine containing derivative. It appears that fluorine compounds, which incidentally, are exceedingly difficult, costly, and hazardous to prepare, are less reactive than the chlorine compound, apparently because a large percentage of the fluorine atoms are more firmly attached than in the instance of the chlorine atom.

The above examples are purely illustrative and by no means exhaust the list of possible reactants or reaction conditions. When chlorinated furfural is used as the base reactant one may utilize as the inorganic reactant such substances as water, ammonia, hydroxylamine, sulphides, iodides, bromides, as well as the alkali and alkaline earth metal salts or compounds of any of the nonmetallic elements including sulphur, selenium, tellurium, phosphorus, nitrogen, etc.

The number of known organic compounds is many times as extensive as the known inorganic compounds. Organic compounds are, therefore, of particular interest as reactants for the halogenated aldehydes of the mono hetero atomic five membered rings for the purpose of producing reactive derivatives. Under appropriate conditions of reaction one may utilize virtually any one of the known organic compounds with the possible exception of compounds such as carbon dioxide, carbon monoxide, carbon terachloride, etc., and even these compounds under appropriate conditions of catalysis and in the presence of another reactant can be utilized in the preparation of reactive derivatives out of the halogenation products of the aldehydes of the mono hetero atomic five membered rings.

It is essential that when the substantially fully saturated halogenation addition products of the aldehydes of the mono hetero atomic five membered rings are reacted the conditions be such that at least one-quarter of the original halide atoms remain in the reaction product otherwise the same will be insufficiently reactive to permit its classification with the herein referred to reactive products. The more powerful dehalogenating agents such as the alkali metals and alkaline earth metals as well as materials such as finely divided iron powder, magnesium powder, zinc powder, etc. are generally speaking too energetic and violent in their action to permit their direct use in the absence of a diluent. The oxides and hydroxides of the alkali metals and alkaline earth metals likewise may be considered as being too energetic to permit their use in the absence of a diluent. Most organic bases, particularly the polyamines, react very violently, sometimes with explosive force with the halogenated aldehydes and in order to achieve an effective control and a uniformity of product, it is necessary to utilize a suitable diluent. As has already been pointed out, alcohols, e. g., methanol, react with the halogenated aldehydes to form ethers and in very many instances such ether formation is not at all undesirable, but to the contrary, is often an advantage. It is, therefore, feasible and convenient to utilize a material such as methanol as the diluent and in this way the said diluent functions at the same time as a reactant. Thus, when sodium hydroxide is brought into contact with chlorinated furfural an exceedingly energetic, erratic, nonuniform and uncontrollable reaction occurs. If, however, the chlorinated furfural be dissolved in methanol and the sodium hydroxide be likewise dissolved in either methanol, aqueous methanol or water, and the same then cautiously added to the methanol solution of the chlorinated furfural, a comparatively smooth reaction occurs. The resultant reaction product will, to be sure, contain some methoxy groups but this in most instances is permissible. In the instance of alcohol insoluble organic products, benzene is often a suitable working medium.

oftentimes it is desirable to perform a series of operations upon the halogenated aldehydes. Thus, one may first react chlorinated furfural with methanol after the manner of some of the above examples and then the resultant reaction product may be further reacted with a reagent of an altogether different nature, e. g., a methanol solution of potassium iodide, sodium sulphide, aniline, ammonia, phenol, urea, etc.

Although the partially dehalogenated reactive derivatives of the present invention are generally procured and isolated as the residuum, it is also possible in many instances to procure the same in the form of a distillate. This is best accomplished by subjecting the material to distillation under very high vacuum or by a molecular still. Chlorinated furfural, upon heat treatment at elevated temperatures under a very high vacuum, largely distills over into a somewhat dehalogenated reactive derivative. The products resulting from the reaction between chlorinated furfural and large quantities of methanol or the reaction products procured by reacting chlorinated furfural with methanol in the presence of calcium carbonate, caustic soda, etc., or finally the products resulting from reaction between chlorinated furfural and a salt such as sodium acetate in the presence of methanol (methoxylated-acylated derivatives) lend themselves more readily to high vacuum distillation than the majority of the other derivatives.

Referring to organic co-reactants, chlorinated furfural, or in its broader aspects the halogenation products of the aldehydes of the mono hetero atomic five membered rings, can be made to react with the aliphatic, carbocyclic and heterocyclic classes of organic compounds. The presence of specific functional groups, such as alcoholic hydroxy groups, phenolic hydroxy groups, carbonyl groups, amino groups, etc. facilitate the reaction. As a consequence, chlorinated furfural will combine more'readily with alcohols, ketones,

esters, amines, acids, nitro-derivatives, etc., than with the parent substances.

Chlorinated furfural can be converted to reac- 231? tiv derivatives' b'y reacting the same withall mannerof aliphatic hydrocarbons whether satu: rated or unsaturated and non-aromatic carbocyclic compounds. It is often'necessary-to use a catalyst such as an" aluminum halide to procure tives by reacting the same with 'alkanes, alkenes,-

alkadien'es, alkapolyenes alkynes, alkadiynes, alkapolynes, cyclanes, spiranes, bicyclanes,-polycyclan'es; cyclen'es, bicyclenes, p'olycyclenes, etc. Chlorinated furfural canreact more readily with compounds containingunsaturated linkages than with the fully saturated compounds. Hydrocarbons that are of a type'thatrea'dily undergo autoreaction, e. g., isomerlzation'or polymerization, generally react either'faster'or more thoroughly than do the less reactive, more stable compounds.

Chlorinated 'furfural can be converted to reactive derivatives by reacting the same with all manner of aromatic:= or'ca'rb'o'cyclic compounds. Here too, the presence'of asuitable catalyst'such' as an aluminum halide is desirable. Thus, the chlorinated furfural can -be-made to rea'ct'with the 'alkyl benzenes, alkenyl benzenes, alkadienyl benzenes, alkapolyenyl benzenes, alkynyl benzenes, as well aswith' the condensed aromatics such as the indanes, indenes, fluorenes, naphthylenes, anthracenes, phenarithrenes, naphthacenes, aromaticc y 'c'l a n e' hydrocarbons, aromaticcyclene hydrocarbons, aromatic-cyclodiene hydrocarbons, etc. All mann'er'of compounds belonging'to the so-calledcl'ass-of terpenes can be made to react quite readily with chlorinatedl furfural to yield partially dechlorinated'reactive derivatives.

The reactive derivatives that are procurable via the reaction of chlorinated furfural with aliphatic orcarb'ocyclic hydrocarbons are of a most diverse nature. As a rule, complicatedmixtures of complex products come into being. In instances the reaction products are'of a stable,

fusible character and in other instances they are" It should b'e notedthat hydrogen chloride is almost invariably engendered-in these In the instance of some or the more non-fusible.

reactions. complex unsaturated hydrocarbons, apart of the hydrogen chloride may be absorbed into thecom plex by Way of an additio'nreaction. Thereac tion'products with but'few exceptions are dark in color} a deep amber, brownish-black and black-4n many'instances; of course, via processes ofdistillation ordecoloration in one manner or another, many of the products can be lightened.

Chlorinated furfural canbe converted to reactive derivatives by reacting the same withall manner of heterocyclic compounds. Specifically we here mention:

Mono-heteroatomic three membered rings" (e: g., ethylene oxide, ethylene sulfide-and ethyl ene imine').

Di-heteroatomic three membered rings (hy-- draziand azomethylene' group, and diazometh rings 24 naphthenes, indoles', diphenylene oxide group; diphenylene sulfide-group, 'dibenzo pyrroles, etc.)

Poly-heteroatomic five membered rings (pyrazoles, indazoles, isoxazoles, indoxazenes, gly-' oxalines, benzoglyoxalines, oxazoles, benzoxazoles,

thiazoles, benzothiazoles, osotriazoles, pyrro-diazoles, furazans, azaximes, oxydiazoles, furodiazoles, thio-diazoles, thio-triazoles, and tetra azoles).

Mono-heteroatomic six membered rings, e. g., six membered rings with an oxygen member (pyrones, benzo derivatives, coumarins, fiavone, luteolin, xanthene, fluoran'es, xanthone, etc.; six-membered rings containing a nitrogen member' (pyridine group, e. g., pyridines, halogen pyridin-es, sulphonic acids, nitropyridines, pyridones, thiopyridines, pyridyl alcohols, pyridyl ketones, pyridine carboxylic acids, oxypyridine carboxylic acids, hydropyridines,- piperideines, piperidines, quinolines, condensed quinolines, isoquinolines, phenanthridines, naphthyridines, quindolines, acridines, anthrapyridines); poly-heteroatomic six membered rings (oxazines, thiazines, diazines, triazines, tetrazines); membered rings which contain both oxygen and sulphur members as well as the vegetable alkaloids.

The reactive products that result from the reaction between chlorinatedfurfural and heterocyclic compounds (often in the presence of a catalyst) are of the most diverse nature imaginable. Generally speaking, however, these reaction products, prior to purification, are dark in color and all contain more or less chlorine. Some of the compounds are' fusible, others are nonfusible, and almost invariably they are of a higher complex nature. These'reaction products like those ofthe other hydrocarbons serve as useful intermediaries for the production of other compounds and are of interest from the standpoint of resins, rubbers, pharmaceuticals, dyestuffs, insecticides, etc., etc.

The introduction of a non-hydrocarbon reactive'functional group into a molecule of a hydrocarbon facilitates the potential reactivity of: the resultant substituted compound with chlorinated furfural. The greater the number of such functional groups present in the molecule of the'reactant; the more readily it reacts. Generally speaking, chlorinated furfural will react with many hydrocarbons which contain non hydrocarbon substituting groups, often quite readily upon heating in the absence of a catalyst; Chlorinated furfural will react in this wise with all manner of non-hydrocarbon substituted organic compounds to yield partially dehalogenated reactivederivatives. It is to be distinctly understood, however, that the reaction conditions as regards the proportionsand the timetemperature schedllle must be deliberately calculat'ed so as not to result in an elimination of genated derivatives of the hydrocarbons, irre-- spective of whether theybe saturated. or unpoly-heteroatomic sixsaturated aliphatic carbocyclic, heterocyclic or mixed.

Chlorinated furfural can be converted over into reactive derivative by reaction with all the oxidation derivatives of the aliphatic hydrocarbons including the monohydric alcohols, unsaturated alcohols, olefine alcohols, acetylene alcohols, diolefine alcohols, simple and mixed ethers and esters of mineral acids, sulphur derivatives of alcohol radicals, selenium, tellurium, nitrogen and phosphorous derivatives of the alcohol radicals, alkyl derivatives of arsenic, antimony, boron, silicon, germanium and tin, metallo organic compounds, all manner of aldehydes whether aliphatic, carbocyclic or heterocyclic, ketones including their halogenation substitution products, peroxides (ethers and esters), sulphur derivatives, nitrogen derivatives, as well as the olefines and diolefine aldehydes and ketones.

Chlorinated iurfural can be converted over into reactive derivatives by reaction with the mono and poly basic carboxylic acids of the saturated and unsaturated type whether aliphatic, carbocyclic or heterocyclic, also their anhydrides and nitriles.

Chlorinated furfural can be quite readily converted over into reactive derivatives by reaction with the dihydric alcohols and their oxidation products, e. g., glycols, (ethers and esters), thio compounds, nitrogen derivatives, aldehyde alcohols, ketone alcohols, ketols, di-aldehydes, ketone aldehydes. di-ketones, carboxylic acids, hydroxy olefine acids, aldehyde acids, ketonic carboxylic acids (whether saturated or unsaturated), as well as their innumerable haloid, sulphur and nitrogen derivatives.

Chlorinated furfural can easily be converted into reactive derivatives by reaction with the trihydric alcohols, di-hydroxy ketones, hydroxy dialdehydes, hydroxy aldehyde ketones, hydroxy ketones, di-aldehyde ketones, aldehyde di-ketones, tri-ketones, di-hydroxy monocarboxylic acids, monoaminocarboxylic acids, monoaminothiocarboxylic dimonoaminocarboxylic acids, dihydroxy olefine monocarboxylic acids as well as their esters, etc.

Chlorinated furfural can be converted over into reactive derivatives by reaction with penta-, hexa-, and poly-hydric alcohols and their oxidation products, e. g., pentitols, aldopentoses, hexitols, heptahydric alcohols, oxyhydric alcohols, monohydric alcohols, polyhydroxy aldehydes and ketones, aldehexoses, ketohexoses, aldoheptoses, aldo-octoses, aldononses, hexaketones, as well as the various carboxylic acids, ethers and esters that are derivable from the above polyhydric alcohols. Included in this category are all the various sugars, starches, etc.

Chlorinated furfural reacts with all manner of proteins and albuminous substances.

Partially dehalogenated reactive derivatives can be procured by reacting chlorinated furfural with substantially any of the derivatives of the carbocyclic compounds, e. g., the derivatives derivable from the tri, tetra, penta, hexa, hepta, octo and mono-carbocyclic compounds. Thus, it can react with the non-hydrocarbon substitution products of the mono-nuclear aromatic substances, e. g., the halogen derivatives, nitrogen derivatives including the nitro and nitroso derivatives, hydroxylamines, nitrosohydroxylamines, analines, diamines, nitrosamines, nitramines, diazo compounds, diazo-amido-compounds', diaZo-oxy-amido compounds, ozoxy compounds, azo compounds and hydrazine compounds. Chlorinated 26 furfural can be made to react with the aromatic compounds of phosphorous, arsenic, antimony, bismuth, boron, silicon, tin as well as with the metal derivatives such as magnesium biphenyl, aryl-magnesium haloids, mercury diphenyls, etc. Chlorinated furfural can react with all the sulfonic acids and all their derivatives, phenols, quinones, aromatic alcohols, and their oxidation products, e. g., the phenyl-parafiin alcohols, aromatic mono-aldehydes, aromatic mono-ketones, aromatic mono-carboxylic acids, and aromatic poly-carboxylic acids as well as their innumerable derivatives including the esters, acids, haloids, acid anhydrides, acid peroxides, thio-acids and bi-thio-acids, acid amides, acid hydrazides, acidyl-azides, nitriles, amido-haloids, imido chlorides, phenyl-hydrazine-imido-chlorides, imidoethers of the aromatic acids, thiamides of the aromatic acids, imido-thio-ethers and the amidines of the aromatic acids, di-oxy-tetra-azotic acids, hydrazidins, nitrazones, nitrotrosazones, phenyl-azoxines, formazyl derivatives, hydroxamic acids, ethers and esters, haloids of the benzohydroxamic acid, benzo-nitrolic acid, benzo-nitrolisic acid, nitrile oxides, amidoximes, hydrazidoximes, hydraxamoximes, ethyl ortho benzoic esters, benzo-trichlorides and trifluorides, ortho benzoic acid piperidides, the various other substituted aromatic acids. Chlorinated furfural can be made to react with the oxy-phenyl-paraflin alcohols and their innumerable alcohols, aromatic oxy mono aldehydes, phenyl ketones, phenyl-carboxylic acids, polyhydric aromatic alcohols in which one or more hydroxyl groups are present in each side chain as well as their oxidation products, aromatic substances with unsaturated side chains, e. g., olefine benzenes, acetylene benzenes, diolefine benzenes, olefine-acetylene-benzenes, olefine-phenoles, acetyl-anisols, phenyl-olefine alcohols, and their oxidation products, oxy-phenyl-olefine-carboxylic acids, as well as the oxidation products of aromatic poly-alcohols with unsaturated side chains, e. g., phenylene-oxy-olefine-carboxylic acids, phenyl-diolefine-a-keto-carboxylic acids, cyano-cinnamic acid, phenylene-oxy-olefine-dicarboxylic acids.

Reactive derivatives may be procured by reacting chlorinated furfural with all manner of hydro-aromatic substances with one or more nuclei including all their, derivatives and substitution products, e. g., the halogen, nitro and amino substitution products of the cyclohexanes, hexa-hydrobenzenes, naphthenes, cyclo-hexanes, tetrahydro-benzenes, naphthylenes, di-hydro-benzenes, cyclo-hexa-dienes, ring alcohols of the hydro-aromatic hydrocarbons, e. g., cyclo-hexanol, quinite, queroite, inosite, phenose, the ring alcohols of the tetra-hydro-benzenes, extra cyclo-hydro-aromatic alcohols as well as their derivatives, ring amines of the hydro-aromatic hydrocarbons, e. g., amiclo-cyclo-hexanes, extra cyclo-hydroaromatic amines, ring ketones of the hydro aromatic hydrocarbons, hydro-aromatic aldehydes, e. g., cyclo citral, extra cyclo-hydro-aromatic ketones, hydro-aromatic carboxylic acids, e. g., hydro-aromatic mono-carboxylic acids, hexa-hydro-oxy-benzoic acids, quinic acid, shikimit acid, succino-succinic acid.

Partially dehalogenated reactive derivatives can be procured by reacting halogenated aldehydes with all manner of terpenes, e. g., the olefinic terpene group (myrcene, coimene, isotrene, as well as their various haloid substitution products, etc.), the olefinic terpene alcohols, olefinic terpene aldehydes, olefinic terpene acids, monocyclic terpenes,-:'e. g :glimonenaiterpinolene; terpinene, phellandrena: alcohols of the monocyclic :terpenes, e. g., menthane alcohols, secondary menthols, tertiary menthols, mono,:-di, and: poly-acid alcohols, bases and ring .-ketones of the mono- .cyclic terpenes. Chlorinated furfural quite readily reacts with the dicyclicterpenes as well as the sesqui terpenes and poly-,terpenes, e. g., thujene, sabinane, carone,-eucarvone, pinene, turpentine oil, terebinic acid, myrtenol, pinol, camphene group comprising camphenebornylene, fenchene, .borneol, iso-borneol, camphor, fenchone, candinene, santalol, caoutchouc.

Reactive derivativesmay be procured by reacting chlorinated furfural with all manner of aromatic hydrocarbons containing several nuclei, e. g., phenyl benzols, and the polyphenyl fatty hydrocarbons and all their derivatives and substitution products including the phenyl-benzoles, benzo-benzoles, triphenyl methanes, phenyl derivatives f the triphenylcarbinols, phenyl-bisdi-phenyl methanes, tetra phenyl methanes, homologous diandpolyphenyl parafiins and the condensed nuclei type and all their derivatives.

-We havealready pointed outthat the presence of a non-hydrocarbon functionally reactive group :ina hydrocarbon molecule further enhances the reactability and the reaction possibilities with the halogenation-:products-of1 the aldehydes of the mono hetero-atomic 'five-membered rings. Specificallyit maybe-statedby way of example that a hydrocarbon.compound-containing one ormore .of the following structural-groupings, complexes, or radicals will in general react either more readily, more thoroughly, or in .a more profound .manner with-the =halogenation products of the aldehydes of the mono hetero'atomic five membered rings thanitsoriginalyprogenitor. *With due consideration :to the quantitative relationships and me ltime-temperature schedule, the ultimate reaction product-will always baa partially -dehalogenated reactive derivative. For convenience, these'functional typical groups have been listedin alphabetical. order:

Hydrazi "Piperonylidene Hydrazino Propargyl 'Hydrazo Propenyl Hydrazono -Propenylidene Hydroxamino Propronyl Isonitroso 'Propylidene Imidazolyl Pyr'azolyl Imino -Pyridyl Iodo Pyridylidene 1o Iodoso Pyrimidyl Iodoxy Pyrroyl Isocyano Pyrryl Isodiazo Selenino Isonitro Seleninyl Isonitroso -Seleno Isothiocyane Selenocyano Isoxazoyl Selenono Keto 'Selenoeyano Lactam 'Selenyl Lactide Semicarbazido Lactone Silicono -Mercapto Silicyl Mercuri -Silicylene Methionyl Stannyl 5 Methylene Stibarseno Methylenedioxy -Stibinoco Methylidyne Stibino -Nitramino Stibo Nitrilo Stibono Nitro Stibos0 Nitroso *Stibylene Oxalyl 'Sulfamino Oxamido Sulfino I Oximido sulfinyl Oxo "Sulfo Oxy Sulfonamide 'Pentazyl Sulfonic Perthio F Sulfonyl I Phenetidimo -Sulfunic Phenolic Telluro 'Phenylaz o "Tetrazyl Phenetyl Theonyl Phenoxy Thiazyl 'Phenylazo *Thio Phenylenediazo Thiocarbonyl 'Phenylidene Thiocyano Phenylureido 'Thiohydroxy 'Phosphorseno -Thiol Phosphazo Thiono 'Phosphinico Thionyl Phosphino Triazeno Phospho 1 Triazinyl 'Phosphono Triazo -Phosphoro Triazolyl Phosphoroso Uramino Phthalal Ureido Phthalamido Ureylene -Phth'alidene Vinyl Picryl -Vinylene Piperidyl Vinylidene *Piperonyl Xanthyl Acetal Boryl Ac'etamido Bromo Acetimido Carbonyl Acid anhydride Carbylamine Acid halide 'Carbonyldi-oxy Alcoholic OHgroup 'Chloro Aldehyde group Chloromercuri Aldo Cyano Alkyl thio Cyanid Amide 'Cyanate Amidoxime Diazo Amino 'Diazo-amino Amine Diazotate Amoxy Diazonium Anilino Diazoxy Antimono -I|I ithio Arseno Disulfide Arsenoso 1 Epoxy Arsinico Ester Arsino P Ether Arso Ethy-lidene Arsono Ethylidyne Arsylene iEthynyl Azimino Ethynylene Azido *Fluoro Azino Formamido Azo Formazyl Azoxy Guanido Benzamido Guanyl Benzimido Halogeno Biphenylenediazo :Hydrazide "-.vManye-oi thelpartially .dehalogenatedreactive derivatives are gsuitableufor further reaction with other reagentsmnddn this -,manner; -.serve as in- .termediateszfori the production ofiii-Wide variety of :materials. ivManysbfu :these; partially 1. dehalogenatedreantive;-de1.'ivativesi are T ."of interest from v10 7 the standpoint:- of resins, :plasticizers, softeners,

- graphic-chemicals;ztanninamaterialsnetc.

As may readily be seen from a study of the above representative list of compounds or classes of compounds with which the chlorinated furfural can be made to react, this latter compound is indeed possessed of an extraordinary reactivity. It is no exaggeration to say that this compound may be made to react with virtually all known organic compounds. This unusual reactivity is, of course, associated with the reactive functional groups that are present in the chlorinated furfural. This unusual reactivity is perhaps anticipatible from a consideration of the fact that even relatively highly stable substances such as ethyl chloride or monochlor benzene can, under appropriate conditions, be made to react or combine with other materials. On the other hand chlorinated furfural contains eight potentially reactive chlorine atoms besides probably containing two other functionally reactive groups (an aldehyde group and an alcoholic hydroxy group). Chlorinated furfural reacts with water or the moisture of the air and with alkaline materials such as ammonia or the alkali metal or alkaline earth oxides or hydroxides or with organic bases such as aniline or polyamino compounds, often in a very violent, almost explosive manner.

Partially dehalogenated reactive derivatives of the halogenation products of the aldehydes of the mono hetero atomic five membered rings may be made by reacting the same with organic materials such as foodstuifs, dyestuffs, pharmaceuticals, tannin materials, photographic chemicals, fuel oils, organic waste products, animal and vegetable oils, turpentines, rosin, various resins of either the thermosetting or thermoplastic types, natural and synthetic rubbers, gums, silks, rayon, cellulose, wool, synthetic linear superpolyamides, e. g., nylon, etc., provided that at least per cent of the halide atoms remains in the resultant compound. It is desirable, though not essential, that the reaction product remain in a. fusible condition.

A study of hundreds of the partially dehalogenated reactive derivatives of the halogenation products of the aldehydes of the mono hetero atomic five membered rings has led the present inventors to conclude that on the whole the reactive derivatives represent complex mixtures containing two or more products. That this is so may be anticipated from a consideration of the fact that the halogenated aldehydes are polyfunctional in character so that if but a single reacting group participates in the reaction, it should be possible to bring into being a plurality of isomerically related compounds. When, for example, methanol reacts with chlorinated furfural so that the mean methoxy content corresponds to say three methoxy groups, there undoubtedly are present compounds that contain one or two methoxy groups on the one hand, and on the other hand, there probably are present compounds that contain more than three groups. In this simple case, if one were to consider the theoretical isomers, it is conceivable that in all such a derivative may contain Well over a hundred distinct chemical compounds. Where a more complex reaction procedure is utilized, it is quite conceivable that the so-called reactive derivative comprises no less than a thousand distinct chemical entities.

From a utilitarian standpoint, the partially dehalogenated reactive derivatives of the halogenation products of the aldehydes of the mono hetero atomic five membered rings are possessed of an extremely diversified field of usefulness.

30 The products per se can, by further reaction, be converted into non-reactive derivatives, which latter are of themselves possessed of a great field of utility.

The partially dehalogenated reactive derivatives of the halogenation products of the aldehydes of the mono hetero atomic five membered rings are highly useful as curing agents for a wide variety of resins including phenol-formaldehyde resins, urea resins, melamine resins, etc. When a reactive derivative is mixed with one of the aforementioned types of resins, it cures, sets up, or hardens the same under the influence of heat to a state of infusibility or thermo rigidity. The reactive derivatives of the present invention can often advantageously be utilized in lieu of hexamethylenetetramine. An extremely wide range of cures can be procured through their use. It is found that a variety of metallic oxides, particularly red iron oxide and to a lesser extent, material such as zinc oxide, antimony oxide, etc., are effective catalysts in speeding up the cure reaction. The inclusion of reactive organic bodies such as nitrophenols, polybasic acids, and anhydrides, e. g., meleic acid, furfuryl alcohol, polyamino compounds, amino hydroxy compounds and poly phenols is often advantageous. One advantage of these reactive derivatives resides in the fact that they can be produced in such a wide variety of physical and chemical properties. In this wise, it is easy to procure a derivative that shall be compatible with or soluble in a given resin or resin solvent.

The partially dehalogenated reactive derivatives of the halogenation products of the aldehydes of the mono hetero atomic five membered rings are extremely useful as curing agents for rubbers, particularly the synthetic variety. Thus, through their use synthetic rubbers are converted or cured to a vulcanized rubbery state without the use of the time-honored vulcanizing agent, sulphur, and without the use of any so-called vulcanization accelerator. In many instances phenomenal results are procurable. Thus, the more powerfu1 of the derivatives permit one to procure tensile strengths of in the order of 6,000 lbs/sq. in. with elongations of 500 per cent or better out of butadiene-acrylonitrile copolymer rubber (I-Iycar OR-15). Such vulcanized stock, besides being much stronger than a corresponding sulphur vulcanizate, is possessed of superior aging qualities and a vastly improved resistance to flex cracking and tearing. The strength of such vulcanizates is practically unaffected by high test aviation gasoline. Butadiene-styrene copolymer rubber, commonly known as Buna S, is also susceptible to vulcanization by these reactive derivatives and here too, in many instances, superior results manifest themselves. Various other types of synthetic rubbers such as the Thiokols, etc., are susceptible to conversion to a vulcanized rubbery state by the use of these reactive derivatives. Fillers, lubricants, pigments, dyes, plasticizers, softeners, extenders, modifiers, and other rubber compounding ingredients may be included in the formulations.

The partially dehalogenated reactive derivatives of the halogenation products of the aldehydes of the mono hetero atomic five membered rings are endowed with the remarkable attribute of being able to cure or convert to a thermo rigid or vulcanized rubbery state organic polymers containing a plurality of hydroxy (OH) groups. Typical of such hydroxylated polymers are those descri ed .in opendin appli ati n, Serial :1 N- .464;8 'filed Nov mbe 94 la amlo ed- :Itthus becomes ;possible;through the use of the herein described reactive derivativesto convert to a thermo rigidor vulcanizedrubbery state afte appro t hv lox la ion. n m a y-h a non-convertible polymers, element convertible polymers, linear polymers-additionor f A polymers, three dimensional polymers, and addition or C polymers. Specifically throu h theuse of, the reactive derivatives,,it becomespossible to cure toa thermorigid or vulcanized rubbery state hydroxylated polymers derived from poly,- coumarones, polyindenes, polystyrenes, .polyacry- ,lates, polymethacrylates, polyolefines, {.polycxymethylenes, polyvinyls, e. g., polyvinylorganic esters, polyvinyl inorganic. esters suchas polyvinyl chloride, vinyl copolymers, polyvinyl ethers, polyvinyl acetals, etc., phenol-aldehyde resinsof the Novolak type, permanently thermoplastic alkyd resins, e. g., dihydric alcohol-dibasic acid 'resins, resinous or rubbery acetylene polymers,

resinous or rubbery hydrocarbon polymers, resin- .ous or rubbery petroleum polymers, and ethylene polymers,etc. Of equal utility are the hydroxylated products derivable from the aforementioned .products but which contain halide, i. e., chlorinatedpolymers, e. g., chlorine containing polycoumarones, chlorine containing polyindenes, chlorine containing polystyrenes, chlorine containing polyacrylates, chlorine containingpoly- -methacrylates, chlorine containing-polyolefines, chlorine containing polyoxymethylenes, chlorine containing polyvinyls, e., g., chlorine containing polyvinyl organic esters, chlorine containing r pol vinyl inorganic esters such ,as chlorine, Ontaining polyvinyl chloride, chlorine containing vinyl copolymers, chlorine containing polyvinyl ethers, chlorine containing polyvinylacetals, etc., chlorine containing phenol-aldehyde resinsv of the Novolak'type, chlorine containing permanently thermoplastioalkydresins, chlorine containing resinous or rubbery acetylene polymers, chlorine containing resinous or rubbery hydrocarbon polymers, chlorine containingresinousor rubbery petroleum polymers, and chlorine containing ethylene polymers, etc. The hydroxylated products derived from polymeric substances resulting from chlorination folloWed by-dechlorination either prioror. subsequent to the poly- .merization are equally suitable. .Often the inclusion of reactive organic bodies such. as poly alcohols, polyamino compounds, amino hydroxy compounds, amino acids, amides, furfural, furfuryl alcohol, methyl furfuryl ,aleohol, natural rubber vulcanization accelerators, etc., is desirable. Sometimes the inclusion of inorganicrnaterials-as typified by red iron oxide, zin oxid e, aluminum oxide, antimony oxide, ,manganese digoxide, etc., is beneficial. Polyvinyl alcohols. poly,-

vinyl alcohol-acetate polymers, .and polyvinyl vacetals such as polyvinyl butyralare very readily cured by the use of these reactive,deri'v atives.

The products of the present invention are able to eifect a cure of all manner of polyamino poly- ,mers whether, they be resinousv .or.-rubbery,- in nature. Included in this category are substances akin to those mentioned in the preceding paragraph, but which in lieu of the hydroxy. (OH) groups contain amino groups .Which .may be ,primary, secondary or inpart atleast even tertiary. Substances such. as glues, albuminoids, proteins, including..modified casein productsand modifiedresinous .or rubbery products fllerived from proteins are .susc eptible to reactionwith the he ei es ri d part a l deh loeqne ed react gerivatives.

T r i d riv t ves SQ Ti Q L D: the-p e ;ent invention areofutility .in elevating; the softfi i oin na 1 hermopla t pmdu ts. Thu ..-b h jud c o u o l c e types o reactive derivatives or their use along withan appropriate coreagent, it is possible to elev a t e ,thesoftening pointof polyvinyl acetate-plastics, polyvinyl chloride plastics, polystyrene plastics, et e oduct of theii enti nticn are also extremely useful in that thy b ring abQl t -,a species ofcure of cellulosic,productsincluding the cellulose ethers, cellulose esters, etc. .(e. g-., cellulose nitrates, cellulose acetate, cellulose pro- ;pionate, cellulose butyrate, cellulose aceto butyrate, cellulose esters of dibasicacids, methyl cellulose, ethyl cellulose, propyl cellulose, butyl cel1u- .lose,;etc.). :SuChprQductscaH be appreciably finsolubilized via the use of'the products of the present invention.

The reactive derivatives are ,usable for .lihe gnanuiacture of resins fromsuchdiverseprqducts as phenols, amines, ;polyamin es, as -,well -as a,yvide variety of naturally occurring substances including vegetable. and animal oils, fats, waxes, gums, resins, etc.

The reactive derivatives, permit the production of an almost limited number ,of,;c hemical ,internediaries which are useful for; the; manufacture .of ,Curing agents, vulcanizing. agents, accelerators, antioxidants, dyestufis, photographic chemicals, synthetic tannin materials, pharmaceuticals, in,- ,secticides, etc., etc.

The partially clehalogenated reactive derivatives of the halogenation products of the ,aldehydes of the mono hetero atomic five membered rings are useful in the preparation of impregnat- ,ing materials, floor coverings, coatings, paints and varnishes, cements, bonding wagents, etc. when used for, these purposes, ,the reactive-derivative may function as a curingaid, as a component ofa resin structure, a plasticizer or as a lmqd fyins a e ;The partially dehalogenated reactive deriva- ,tives-of the halogenationproducts-of the aldehydes of the mono hetero atomic-five membered Tin s constitute a unique; and. distinct class. .of substances. The materials may be variously characterized. ,Thus, they maybe characterized as to their derivation inasmuch as the only known means whereby these materials can be synthesized is by. way of the-halogenation products ,of thealdehydes of themono hetero atomic five -membered-. rings. They are iurther characterized in that they retain not less than 25 per cent of, the original halide. atoms containedin .the saturated halogenated aldehydes from which theymare derived. :The products of thepresent invention can ,alsobe characterized-in.termsef their, reactivity. Thus, they all.enter-into reaction with substances .such ,as .tetraethylene .pentamine.

, Itis thought to-be clear from the foregoing disclosure ,that the partially dehalogenated reactive derivatives of the halogenationproducts of the aldehydes of the .mono hetero atomic five membered rings and particularly the derivativespf chlorinated furiural and its. immediate-homo.- logues and analogues constitute amovelv and .upiq a of hemi l'subs ance p s sse of an extremely-wide-range of chemical andphysical properties and having exceedingly-wide range of industrial applications. The .reactive derivatives are .useful in the; manufacture pr;.prepara.-

33 tion of such variedproducts as the followingfor convenience listed alphabetically:

Abrasive articles Lamp basing cements Acidic catalysts Leather substitutes Printing plate matrixes Printing plates Proofin-gs to water, oil,

Cleansing agents Coupling agents Curing agents Dyestuffs etc.

Electrical insulation Repellents Enamels Resins Explosives Rubber substitutes Extenders for resins, Rubber vulcanization plastics, rubbers, etc. accelerators Fillers for resins, rub- Rusting agents bers, etc. Solvents Floor coverings Frictional elements stiffening agents Synthetic and natural Frictionings rubbers Fungicides Synthetic fibers General reactants Tanning agents Germicides Textiles Glues Ultra reactive co-re- Gums agents Hardening agents Varnishes Impregnating agents Vesicants Inks Insecticides The invention has been described in connection with a number of illustrative embodiments, materials, proportions, conditions and arrangements of operations for carrying out the invention. It is, therefore, to be understood that the invention is not to be restricted to the foregoing disclosure, and that no limitations are to be imported required by the language of the appended claims and the state of the prior art. It is further to be understood that the invention is not dependent upon any explanations or theories which have been set forth as descriptive of the actions involved, nor dependent upon the accuracy or soundness of any theoretical statements so advanced.

We claim:

1. The method of producing reactive halogen containing organic compounds which consists in dehalogenating substantially fully saturated halogenation addition products of the aldehydes of the monoheteroatomic five membered rings to a point where the average halogen content of the resultant partial dehalogenation product is equal to not less than one atom of halogen per molecule of aldehyde that entered into the making of the aforesaid saturated halogenation addition prodnot.

2. The method of producin reactive chlorine containing organic compounds which consists in dehalogenating substantially fully saturated chlorination addition products of the aldehydes of the monoheteroatomic five membered rin s to a point where the average chlorine content of the resultant partial dehalogenation product is equal to not less than one atom of chlorine per molecule of aldehyde that entered into the making of the aforesaid saturated chlorination addition product.

Vulcanizing agents 3. The method of producing reactive bromine containin organic compounds which consists in dehalogenating substantially fully saturated bromination addition products of the aldehydes of the monoheteroatomic five membered'rings to a point where the average bromine content of the resultant partial dehalogenation product is qual to not less than one atom of bromine per molecule of aldehyde that entered into the making of the fcresaid saturated bromination addition product.

4. The method of producing reactive iodine containing organic compounds which consists in dehalogenating substantially fully saturated iodination addition products of the aldehydes of the zz-ionoheteroatomic five membered rings to a point where the average iodine content of the resultant partial dehalogenation product is equal to not less than one atom of iodine per molecule of aldehyde that entered into the making of the aforesaid saturated iodination addition product.

5. Reactive halogen containing organic compounds produced by the method which consists in dehalogenating substantially fully saturated halogenation addition products of the aldehydes cf the monoheteroatomic five membered rings to a point where the average halogen content of the resultant partial dehalogenation product is equal to not less than one atom of halogen per molecule of aldehyde that entered into the making of the aforesaid saturated halogenation addition product.

6. Reactive chlorine containing organic compounds produced by the method which consists in dehalogenating substantially fully saturated chlorination addition products of the aldehydes of the monoheteroatomic five membered rings to a point wher the average chlorine content of the resultant partial dehalogenation product is equal to not less than one atom of chlorine per molecule of aldehyde that entered into the making of the aforesaid saturated chlorination addition product.

7. Reactive bromine containing organic compounds produced by the method which consists in dehalogenating substantially fully saturated bromination addition products of the aldehydes of the monoheteroatomic five membered rings to a point where the average bromine content of the resultant partial dehalogenation product is equal to not less than one atom of bromine per molecule of aldehyde that entered into the making of the aforesaid saturated bromination addition product.

8. Reactive iodine containing organic compounds produced by the method which consists in dehalogenating substantially fully saturated iodination addition products of the aldehydes of the monoheteroatomic five membered rings to a point Where the average iodine content of the resultant partial dehalogenation product is equal to not less than one atom of iodine per molecule of aldehyde that entered into the making of the aforesaid saturated iodination addition product.

EMIL E. NOVOTNY. GEORGE: KARL VOGELSANG.

REFERENCES CITED The following referenlces are of record in the file of this patent:

UNITED STATES PATENTS Name Date Richardson Sept. 4, 192

Number (Other references on following page) PAWS Jom'nal Organic Chemistry, vol. 6, Jan. 1941,

7 pgs. 157-, 159, 161 1:) 167. z tz Lam g nf Mar 3 i '194 Chem. Abstracts 1935, page 4354. 2345966 Fiedler 1944 Chem. Abstracts 1930, page 1859. Chem. Abstracts 1933, page 2442. OTHER REFERENCES Chem. Abstracts 1931, page 4880.

Recueilddes Travaux Chimiques des Pays-Has, V01. 50, pages 833 to 836 (1931) by Bilman 8: Wright. 

